JP5386073B2 - Water-based clear coating composition and method for producing coating film using the same - Google Patents
Water-based clear coating composition and method for producing coating film using the same Download PDFInfo
- Publication number
- JP5386073B2 JP5386073B2 JP2007212868A JP2007212868A JP5386073B2 JP 5386073 B2 JP5386073 B2 JP 5386073B2 JP 2007212868 A JP2007212868 A JP 2007212868A JP 2007212868 A JP2007212868 A JP 2007212868A JP 5386073 B2 JP5386073 B2 JP 5386073B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- coating composition
- coating film
- amine compound
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Description
本発明は、建造物の外壁などの塗装に好適に使用される水系クリヤー塗料組成物、およびこれを用いた塗膜の製造方法に関する。 The present invention relates to a water-based clear coating composition that is suitably used for painting exterior walls of buildings, and a method for producing a coating film using the same.
建造物の外壁などの表面（被塗布面）には、意匠性の付与や保護を目的としてクリヤー塗料が塗布される場合が多い。
しかし、クリヤー塗料は、無色透明またはそれに近い透明であるため、クリヤー塗料が塗布された面と未塗布の面においての境界が判別しにくく、塗り忘れや塗り斑といったクリヤー塗料ならではの問題があった。特に光触媒機能を有するクリヤー塗料の場合、防汚性塗膜を形成できるが、塗り忘れが発生すると、その部分では防汚性塗膜が形成されないため所望の光触媒効果が発揮されず、汚れが目立ちやすくなる。
In many cases, a clear coating is applied to a surface (surface to be coated) such as an outer wall of a building for the purpose of imparting designability or protection.
However, since the clear paint is colorless and transparent, or transparent, it is difficult to distinguish the boundary between the surface where the clear paint is applied and the surface where the clear paint is not applied. . In particular, in the case of a clear paint having a photocatalytic function, an antifouling coating film can be formed. It becomes easy.
そこで、特許文献１には、有機系着色剤（有機顔料、有機染料、着色試薬のうち少なくとも１種類以上）を含むクリヤー型の光触媒塗料が開示されている。該光触媒塗料によれば、有機系着色剤によって塗料が着色しているため、塗布の際には塗装部分が目視にて確認でき塗り忘れや塗り斑を防止し、塗布後には光触媒機能によって有機系着色剤を分解して塗膜を脱色することができる。
しかしながら、特許文献１に記載のように、光触媒機能を利用したクリヤー塗料では、形成された塗膜は光触媒機能によって脱色するので、直射日光が当たりにくい部位では直射日光が当たる部位に比べて有機系着色剤が分解されにくく、塗膜の脱色が完了するのに数日〜数週間の時間が必要であった。そのため、無色部分と着色部分との色斑が長時間続くこととなり、外観上問題があった。
また、このようなクリヤー塗料は光触媒塗料に限定されるため、用途が制限されやすかった。
However, as described in Patent Document 1, in the clear paint using the photocatalytic function, the formed coating film is decolorized by the photocatalytic function, and therefore, the organic system is compared with the part that is exposed to direct sunlight in the part that is not easily exposed to direct sunlight. The colorant was hardly decomposed, and it took several days to several weeks to complete the decolorization of the coating film. Therefore, the color spots of the colorless portion and the colored portion last for a long time, and there is a problem in appearance.
Moreover, since such a clear coating material is limited to a photocatalyst coating material, its application is likely to be limited.
本発明は上記事情を鑑みてなされたもので、塗布した部位に関わらず均一、かつ短時間で脱色する塗膜を形成でき、塗り忘れや塗り斑を防止できる水系クリヤー塗料組成物、およびこれを用いた塗膜の製造方法の実現を目的とする。 The present invention has been made in view of the above circumstances, an aqueous clear coating composition that can form a uniform and decolored coating film in a short time regardless of the applied site, and can prevent forgetting to apply or smear, and It aims at realization of the manufacturing method of the used paint film.
本発明者らは鋭意検討した結果、アルカリ水溶液中で赤く呈色し、中性に近づくに連れて無色に変化するフェノールフタレインの特性に着目した。そこで、水系クリヤー塗料組成物の成分として、数多くの種類が存在する指示薬の中から、特にフェノールフタレインを選択して用い、かつアルカリ性になるように塩基性物質（水溶性アミン化合物）を用いてｐＨ値を調整することにより、水系クリヤー塗料組成物が赤く着色するので、塗布の際には塗り忘れや塗り斑を防止でき、塗布後の塗膜の水分の蒸発や、塩基性物質の揮発により、ｐＨ値が中性に近づくことで塗膜が脱色することを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have focused on the characteristics of phenolphthalein that turns red in an alkaline aqueous solution and changes to colorless as it approaches neutrality. Therefore, as a component of the water-based clear coating composition, among the many types of indicators, particularly phenolphthalein is selected and used, and a basic substance (water-soluble amine compound) is used so as to be alkaline. By adjusting the pH value, the water-based clear coating composition is colored red, so it is possible to prevent forgetting to apply and smears when applying, and by evaporating the water content of the coating film and volatilizing basic substances after application. The inventors have found that the coating film is decolored when the pH value approaches neutral, and have completed the present invention.
すなわち、本発明の水系クリヤー塗料組成物は、バインダー樹脂と、沸点が１００℃以上の水酸基を１つ有する水溶性アミン化合物と、フェノールフタレインとを含有し、ｐＨ値が９．５〜１３．０であることを特徴とする。
さらに、光触媒粒子または体質顔料を含有することが好ましい。
That is, the water-based clear coating composition of the present invention contains a binder resin, a water-soluble amine compound having one hydroxyl group having a boiling point of 100 ° C. or higher, and phenolphthalein, and has a pH value of 9.5-13. It is 0.
Furthermore, it is preferable to contain photocatalyst particles or extender pigments.
また、前記水溶性アミン化合物の含有量が、当該水系クリヤー塗料組成物１００質量％中、０．５〜７質量％であることが好ましい。 Moreover, it is preferable that content of the said water-soluble amine compound is 0.5-7 mass% in 100 mass% of the said water-based clear coating composition.
また、本発明の塗膜の製造方法は、前記水系クリヤー塗料組成物を、対象物の被塗布面に塗布した後に、脱色させたことを特徴とする。 The coating film production method of the present invention is characterized in that the water-based clear coating composition is decolorized after being applied to the surface to be coated of the object.
本発明の水系クリヤー塗料組成物、およびこれを用いた塗膜の製造方法によれば、塗布した部位に関わらず均一、かつ短時間で脱色する塗膜を形成でき、塗り忘れや塗り斑を防止できる。
また、本発明によれば、塗布した部位に関わらず塗膜が速やかに脱色するので、無色部分と着色部分とで発生する色斑が短時間（例えば２４時間以内）で解消できる。
さらに、本発明水系クリヤー塗料組成物は、光触媒塗料に限定されない。
According to the water-based clear coating composition of the present invention and the method for producing a coating film using the same, it is possible to form a coating film that can be uniformly and decolored in a short time regardless of the applied site, thereby preventing forgetting to paint or smearing. it can.
In addition, according to the present invention, the coating film is quickly decolored regardless of the applied site, so that color spots occurring in the colorless portion and the colored portion can be eliminated in a short time (for example, within 24 hours).
Furthermore, the water-based clear coating composition of the present invention is not limited to a photocatalytic coating.
以下、本発明について詳細に説明する。
本発明の水系クリヤー塗料組成物（以下、「塗料組成物」という。）は、バインダー樹脂と、水溶性アミン化合物と、フェノールフタレインとを含有する。
また、塗料組成物のｐＨ値は９．５〜１３．０であり、９．６〜１１．０が好ましく、１０．０〜１０．５がより好ましい。ｐＨ値が上記範囲内であれば後述するフェノールフタレインが赤く呈色するので、塗料組成物も赤く着色する。ｐＨ値が上記範囲より中性側に移動すると、フェノールフタレインが赤く呈色しにくくなる（塗料組成物が無色になる）ので、塗料組成物を塗布する際に塗布面と未塗布面との境界が目視にて判断しにくくなり、塗り忘れや塗り斑を防止できにくくなる。一方、ｐＨ値が上記範囲よりアルカリ性になっても、フェノールフタレインの構造が変化して塗料組成物が無色になる。
Hereinafter, the present invention will be described in detail.
The water-based clear coating composition of the present invention (hereinafter referred to as “coating composition”) contains a binder resin, a water-soluble amine compound, and phenolphthalein.
The pH value of the coating composition is 9.5 to 13.0, preferably 9.6 to 11.0, and more preferably 10.0 to 10.5. If the pH value is within the above range, phenolphthalein, which will be described later, is colored red, and the coating composition is also colored red. When the pH value moves to the neutral side from the above range, the phenolphthalein becomes red and difficult to color (the coating composition becomes colorless). Therefore, when applying the coating composition, The boundary becomes difficult to judge visually, and it becomes difficult to prevent forgetting to paint or smear. On the other hand, even if the pH value becomes more alkaline than the above range, the structure of phenolphthalein changes and the coating composition becomes colorless.
＜バインダー樹脂＞
前記バインダー樹脂としては、水性塗料として使用可能なものであれば特に限定されず、例えば、アクリル樹脂、シリコーン樹脂、アクリル−シリコーン樹脂、フッ素樹脂、エポキシ樹脂、酢酸ビニル樹脂、フェノール樹脂、ウレタン樹脂、ポリスチレン樹脂、メラミン樹脂、ケトン樹脂、酢酸ビニル−アクリル樹脂、エチレン−酢酸ビニル樹脂、スチレン−アクリレート樹脂などが挙げられる。中でもアクリル樹脂、アクリル−シリコーン樹脂が好ましい。これらのバインダー樹脂は１種単独で用いてもよく、２種以上を併用してもよい。
<Binder resin>
The binder resin is not particularly limited as long as it can be used as a water-based paint. For example, acrylic resin, silicone resin, acrylic-silicone resin, fluorine resin, epoxy resin, vinyl acetate resin, phenol resin, urethane resin, Examples include polystyrene resin, melamine resin, ketone resin, vinyl acetate-acrylic resin, ethylene-vinyl acetate resin, and styrene-acrylate resin. Of these, acrylic resins and acrylic-silicone resins are preferred. These binder resins may be used alone or in combination of two or more.
バインダー樹脂の含有量（固形分換算）は、塗料組成物１００質量％中、２〜５０質量％が好ましく、４〜２０質量％がより好ましい。バインダー樹脂の含有量が上記範囲内であれば、形成する塗膜の膜厚が均一になりやすくなる。 2-50 mass% is preferable in 100 mass% of coating compositions, and, as for content (solid content conversion) of binder resin, 4-20 mass% is more preferable. If content of binder resin is in the said range, the film thickness of the coating film to form will become uniform easily.
＜水溶性アミン化合物＞
本発明においては、塗料組成物に水溶性アミン化合物を含有させることで、当該塗料組成物のｐＨ値を上記範囲に調整することができる。なお、非水溶性のアミン化合物を用いると、塗料組成物のｐＨ値を上記範囲に調整することが困難となり、塗料組成物が赤く着色しにくくなるので、アミン化合物としては、水溶性のものを用いるものとする。
<Water-soluble amine compound>
In this invention, the pH value of the said coating composition can be adjusted to the said range by containing a water-soluble amine compound in a coating composition. If a water-insoluble amine compound is used, it becomes difficult to adjust the pH value of the coating composition to the above range, and the coating composition is difficult to be colored red. Shall be used.
前記水溶性アミン化合物は沸点が１００℃以上であり、１２０〜２４０℃が好ましい。沸点の下限値が上記値より小さくなると、塗料組成物に含まれる水分との共沸効果による揮発速度が速くなり、塗料組成物を塗布した直後から水溶性アミン化合物が揮発し始めるので、ｐＨ値が上記範囲より低くなる。後述するフェノールフタレインはｐＨ値が上記範囲内の時に赤く呈色するので、塗料組成物は塗布した直後から脱色しやすく、塗布面と未塗布面との境界が目視にて判断しづらくなり、塗り忘れや塗り斑の防止といった本発明の効果を十分に発揮しにくくなる。
一方、沸点の上限値が上記値より大きくなると、水溶性アミン化合物が揮発しにくいため塗膜中に残留しやすくなり、塗膜が黄変したりタック感が残ったりする場合がある。また、塗料組成物に光触媒粒子などの顔料が含まれる場合は、耐防汚性が低下することもある。
The water-soluble amine compound has a boiling point of 100 ° C. or higher, preferably 120 to 240 ° C. When the lower limit of the boiling point is smaller than the above value, the volatilization rate due to the azeotropic effect with moisture contained in the coating composition increases, and the water-soluble amine compound starts to volatilize immediately after the coating composition is applied. Becomes lower than the above range. Since the phenolphthalein described later is colored red when the pH value is within the above range, the coating composition is easily decolorized immediately after application, and the boundary between the coated surface and the uncoated surface is difficult to visually determine. The effects of the present invention, such as forgetting to paint and prevention of smear, are not sufficiently exhibited.
On the other hand, when the upper limit of the boiling point is larger than the above value, the water-soluble amine compound is less likely to volatilize, so that it tends to remain in the coating film, and the coating film may turn yellow or have a tacky feeling. Moreover, when pigments, such as photocatalyst particle | grains, are contained in a coating composition, antifouling resistance may fall.
なお、水溶性アミン化合物は沸点が高くなると、分子量も大きくなる傾向にあり、ｐＨ値を所望の値に調整するのが困難となる傾向にある。従って、ｐＨ値を所望の値に調整するためには配合量を増やす必要があるが、配合量を増やしてもｐＨ値を１０以上に調整することは困難である。そのため、僅かな量の水溶性アミン化合物の揮発でも塗膜の中のｐＨ値は上記範囲を下回るため、比較的短時間で塗膜の脱色が完了する。しかし、脱色後の塗膜中には多量の水溶性アミン化合物が残留するため、塗膜が黄変したりタック感が残ったりしやすくなる。 In addition, the water-soluble amine compound tends to increase the molecular weight as the boiling point increases, and it tends to be difficult to adjust the pH value to a desired value. Therefore, in order to adjust the pH value to a desired value, it is necessary to increase the blending amount, but it is difficult to adjust the pH value to 10 or more even if the blending amount is increased. Therefore, even if a small amount of the water-soluble amine compound is volatilized, the pH value in the coating film is below the above range, so that the decolorization of the coating film is completed in a relatively short time. However, since a large amount of water-soluble amine compound remains in the coating film after decolorization, the coating film tends to turn yellow or feel tacky.
このような水溶性アミン化合物としては、例えば、２−アミノ−２−メチル−１−プロパノール、２−（メチルアミノ）エタノール、３−アミノ−１−プロパノール、Ｎ−メチルジエタノールアミン、トリエタノールアミンなどが挙げられる。中でも、２−アミノ−２−メチル−１−プロパノール、２−（メチルアミノ）エタノール、３−アミノ−１−プロパノールが好ましく、２−アミノ−２−メチル−１−プロパノールが特に好ましい。これら水溶性アミン化合物は、１種単独で用いてもよく、２種以上を併用してもよい。 Examples of such water-soluble amine compounds include 2-amino-2-methyl-1-propanol, 2- (methylamino) ethanol, 3-amino-1-propanol, N-methyldiethanolamine, and triethanolamine. Can be mentioned. Among these, 2-amino-2-methyl-1-propanol, 2- (methylamino) ethanol, and 3-amino-1-propanol are preferable, and 2-amino-2-methyl-1-propanol is particularly preferable. These water-soluble amine compounds may be used alone or in combination of two or more.
なお、水溶性アミン化合物は、仮に沸点が同じであったとしても、含有する水酸基の数が増えるに連れて揮発性が低下する傾向にある。水酸基を複数有する水溶性アミン化合物は塗膜中に残留しやすくなったり、塗膜の耐水性を低下させたりする場合もあるので、水溶性アミン化合物としては、水酸基を１つ有するものを用いるのが好ましい。 Even if the water-soluble amine compound has the same boiling point, the volatility tends to decrease as the number of hydroxyl groups contained increases. Since a water-soluble amine compound having a plurality of hydroxyl groups tends to remain in the coating film or may reduce the water resistance of the coating film, a water-soluble amine compound having one hydroxyl group is used. Is preferred.
水溶性アミン化合物の含有量は、塗料組成物１００質量％中、０．３質量％以上が好ましい。水溶性アミン化合物の含有量が０．３質量％未満になると、塗料組成物のｐＨ値を上記範囲内に調整することが困難となり、フェノールフタレインが赤く呈色しにくくなり、結果、塗料組成物も着色しにくくなる。
ただし、水溶性アミン化合物の含有量が増えると、塗膜が脱色するのに要する時間が長くなる傾向にあるので、無色部分と着色部分とで発生する色斑の抑制を考慮すると、水溶性アミン化合物の含有量は０．５〜７質量％がより好ましい。
The content of the water-soluble amine compound is preferably 0.3% by mass or more in 100% by mass of the coating composition. When the content of the water-soluble amine compound is less than 0.3% by mass, it is difficult to adjust the pH value of the coating composition within the above range, and phenolphthalein is difficult to be colored red. As a result, the coating composition Things are also difficult to color.
However, as the content of the water-soluble amine compound increases, the time required for the coating to be decolored tends to increase. Therefore, considering the suppression of color spots occurring in the colorless and colored portions, the water-soluble amine As for content of a compound, 0.5-7 mass% is more preferable.
＜フェノールフタレイン＞
フェノールフタレインは、酸塩基指示薬として一般的に用いられており、アルカリ性の水溶液中で赤く呈色し、水溶液が中性になるに連れて、また、水分の揮発によりイオンが消失するに連れて無色に変化する。本発明では、この特性を利用しており、上述した水溶性アミン化合物によりｐＨ値を上記範囲に調整したバインダー樹脂の水性エマルションにフェノールフタレインを添加することで、塗料組成物を赤く着色させている。従って、塗料組成物を塗布する際は塗布面と未塗布面との境界が目視にて容易に判断できるようになるため、塗り忘れや塗り斑を防止できる。そして、塗膜中の溶媒（水）の揮発によりイオンが消失することや、水溶性アミン化合物が揮発することで塗膜のｐＨ値が中性側に移動し、フェノールフタレインが無色に変化することで塗膜が脱色する。
なお、本発明において「イオンが消失する」とは、水を構成する水素イオンや水酸化物イオンの消失、およびフェノールフタレイン自身のイオン性の消失を意味する。
<Phenolphthalein>
Phenolphthalein is commonly used as an acid-base indicator and turns red in an alkaline aqueous solution, as the aqueous solution becomes neutral, and as ions disappear due to moisture volatilization. It turns colorless. In the present invention, this characteristic is utilized, and the coating composition is colored red by adding phenolphthalein to an aqueous emulsion of a binder resin whose pH value is adjusted to the above range with the above-described water-soluble amine compound. Yes. Therefore, when the coating composition is applied, the boundary between the coated surface and the uncoated surface can be easily determined visually, so that it is possible to prevent forgetting to paint or smear. And the ion disappears due to the volatilization of the solvent (water) in the coating film, or the water-soluble amine compound volatilizes, the pH value of the coating film moves to the neutral side, and the phenolphthalein changes to colorless. As a result, the coating film is decolorized.
In the present invention, “ion disappears” means disappearance of hydrogen ions and hydroxide ions constituting water, and disappearance of ionicity of phenolphthalein itself.
なお、フェノールフタレイン以外にも多くの指示薬が知られているが、他の指示薬は色の変化を引き起こすことはできるものの、フェノールフタレインのような容易な機構では無色になりにくく、クリヤー塗料組成物本来の効果が発揮されにくくなる。
従って、本発明では、指示薬としてフェノールフタレインを用いるものとする。
なお、フェノールフタレインは水に難溶であるため、通常、エタノールやプロパノールなどのアルコールに溶解させ、さらに必要に応じて水で希釈して用いる。
Many indicators other than phenolphthalein are known, but other indicators can cause a color change, but it is difficult to become colorless by an easy mechanism such as phenolphthalein, and clear paint composition The original effect is difficult to be demonstrated.
Accordingly, in the present invention, phenolphthalein is used as an indicator.
Since phenolphthalein is hardly soluble in water, it is usually dissolved in an alcohol such as ethanol or propanol and further diluted with water as necessary.
フェノールフタレインの含有量（固形分換算）は、塗料組成物１００質量％中、０．０１〜０．５質量％が好ましく、０．０３〜０．３質量％がより好ましい。フェノールフタレインの含有量の下限値が上記値より小さくなると、塗料組成物のｐＨ値が上記範囲内であったとしても赤く着色しない場合がある。一方、フェノールフタレインの含有量の上限値が上記値より大きくなっても、着色効果に変化はなく、製造コストが増加する。 The content of phenolphthalein (in terms of solid content) is preferably 0.01 to 0.5% by mass and more preferably 0.03 to 0.3% by mass in 100% by mass of the coating composition. When the lower limit of the content of phenolphthalein is smaller than the above value, the coating composition may not be colored red even if the pH value of the coating composition is within the above range. On the other hand, even if the upper limit value of the content of phenolphthalein is larger than the above value, there is no change in the coloring effect and the production cost increases.
＜顔料＞
本発明の塗料組成物には、顔料を含有させてもよい。顔料としては、光触媒粒子や体質顔料などが挙げられるが、中でも光触媒粒子が好ましい。塗料組成物に光触媒粒子を含有させることで、塗料組成物の成分に用いる水溶性アミン化合物の沸点が高かったり、含有量が多かったりして、水溶性アミン化合物が塗膜中に残留したとしても、光触媒粒子が水溶性アミン化合物やフェノールフタレインを分解するので、塗膜が速やかに脱色すると共に、耐水性の低下をより抑制できる。さらに、塗膜に付着した埃や汚れなどの有機物を、光触媒粒子が分解するので、塗膜に防汚性機能をも付与できる。
<Pigment>
The coating composition of the present invention may contain a pigment. Examples of the pigment include photocatalyst particles and extender pigments, among which photocatalyst particles are preferable. Even if the water-soluble amine compound remains in the coating film because the water-soluble amine compound used as a component of the coating composition has a high boiling point or a high content by containing the photocatalyst particles in the coating composition. Since the photocatalyst particles decompose the water-soluble amine compound and phenolphthalein, the coating film can be quickly decolorized and the water resistance can be further prevented from decreasing. Furthermore, since the photocatalyst particles decompose organic substances such as dust and dirt adhering to the coating film, it is possible to impart an antifouling function to the coating film.
このような光触媒粒子としては、酸化チタンなどが挙げられるが、中でもアパタイトなどのリン酸カルシウムが酸化チタンに被覆した光触媒複合粒子が特に好ましい。アパタイトは、タンパク質やアルデヒド類などの物質吸着能に優れているため、光がなくても物質を吸着できる上、光が照射された時に吸着しておいた物質を光触媒機能により分解することができる。従って、上述した光触媒複合粒子を含有させることで、塗膜の防汚性がより向上する。
なお、アパタイトは、酸化チタンの表面を完全に被覆しているのではなく分散して析出しているので、酸化チタンの表面は部分的に露出しており、光触媒機能はほとんど失われることはない。また、酸化チタンの表面をアパタイトが被覆していることで、アパタイトがスペーサーとなり、酸化チタンとバインダー樹脂とは直接接触しにくくなるため、バインダー樹脂は分解されにくい。
光触媒複合粒子としては、市販のものを用いることができ、例えば、石原産業社製のＳＴシリーズなどが好適である。
Examples of such photocatalyst particles include titanium oxide. Among them, photocatalyst composite particles in which calcium phosphate such as apatite is coated on titanium oxide are particularly preferable. Apatite has excellent ability to adsorb substances such as proteins and aldehydes, so it can adsorb substances without light and can decompose the adsorbed substances by photocatalytic function when irradiated with light. . Therefore, the antifouling property of a coating film improves more by containing the photocatalyst composite particle mentioned above.
In addition, since the apatite is not completely covering the surface of the titanium oxide but is dispersed and deposited, the surface of the titanium oxide is partially exposed and the photocatalytic function is hardly lost. . Further, since the surface of titanium oxide is coated with apatite, the apatite serves as a spacer, and the titanium oxide and the binder resin are difficult to directly contact with each other, so that the binder resin is not easily decomposed.
As the photocatalyst composite particles, commercially available particles can be used, and for example, ST series manufactured by Ishihara Sangyo Co., Ltd. is suitable.
顔料として例えば前記光触媒複合粒子を含有させる場合、その含有量は、塗料組成物１００質量％中、０．１〜１０質量％が好ましく、０．３〜５質量％がより好ましい。光触媒複合粒子の含有量の下限値が上記値より小さくなると、光触媒の効果が発現しにくくなる。一方、光触媒複合粒子の含有量の上限値が上記値より大きくなると、塗膜の耐候性が低下しやすくなる。 For example, when the photocatalyst composite particles are contained as a pigment, the content thereof is preferably 0.1 to 10% by mass and more preferably 0.3 to 5% by mass in 100% by mass of the coating composition. When the lower limit value of the content of the photocatalyst composite particles is smaller than the above value, the effect of the photocatalyst is hardly exhibited. On the other hand, when the upper limit of the content of the photocatalyst composite particles is larger than the above value, the weather resistance of the coating film tends to be lowered.
＜その他＞
本発明の塗料組成物には、本発明の趣旨を逸脱しない範囲内で、造膜助剤や各種添加剤が必要に応じて含まれていてもよい。
造膜助剤としては、具体的には、テキサノール、ブチルセルソルブ、ブチルセルソルブアセテート、カルビトール、トリエチレングリコール等を例示することができる。これらの各種造膜助剤は１種単独で用いてもよく、２種以上を併用してもよい。造膜助剤の含有量は、塗料組成物１００質量％中、０．１〜１０質量％が好ましい。
添加剤としては、消泡剤、増粘剤、凍結安定剤、湿潤剤、浸透助剤、防藻剤、防カビ剤、防腐剤等、通常の塗料に用いられる添加剤が適宜使用できる。
<Others>
The coating composition of the present invention may contain a film-forming aid and various additives as necessary within the range not departing from the gist of the present invention.
Specific examples of film-forming aids include texanol, butyl cellosolve, butyl cellosolve acetate, carbitol, triethylene glycol, and the like. These various film-forming aids may be used alone or in combination of two or more. The content of the film-forming auxiliary is preferably 0.1 to 10% by mass in 100% by mass of the coating composition.
As additives, additives used in ordinary paints such as antifoaming agents, thickeners, freezing stabilizers, wetting agents, penetration aids, algaeproofing agents, fungicides, and preservatives can be used as appropriate.
＜塗料組成物＞
本発明の塗料組成物は、上述したバインダー樹脂に、必要に応じて顔料、造膜助剤、および各種添加剤を加え、さらに水を加えて撹拌混合した混合物に、水溶性アミン化合物を添加してｐＨ値を調整した後、フェノールフタレイン溶液を添加することで得られる。
各成分を上述した含有量の範囲内で添加することにより、フェノールフタレインが赤く呈色し、赤く着色した塗料組成物が得られる。
水の含有量は、塗料組成物１００質量％中、５０〜９８質量％が好ましく、８０〜９６質量％がより好ましい。
<Coating composition>
In the coating composition of the present invention, a pigment, a film-forming aid, and various additives are added to the binder resin as described above, and a water-soluble amine compound is added to a mixture obtained by adding water and stirring. After adjusting the pH value, it is obtained by adding a phenolphthalein solution.
By adding each component within the above-described content range, phenolphthalein is colored red, and a red-colored coating composition is obtained.
50-98 mass% is preferable in 100 mass% of coating compositions, and, as for content of water, 80-96 mass% is more preferable.
なお、バインダー樹脂は、予めエマルションにしてから用いてもよい。エマルションに調製する方法としては、特に制限はなく、例えば、バインダー樹脂の原料モノマーを、水溶媒を使用した乳化重合法などで重合させることにより、水中において樹脂微粒子が乳化、分散したエマルションを得ることができる。また、エマルションとしては市販のものを用いてもよく、例えば、旭化成ケミカルズ社製のポリデュレックスシリーズなどが好適である。
なお、エマルション１００質量％中におけるバインダー樹脂の質量割合には特に制限はないが、好ましくは２０〜６５質量％程度とする。
In addition, you may use binder resin, after making it into an emulsion beforehand. The method for preparing the emulsion is not particularly limited, and for example, an emulsion in which resin fine particles are emulsified and dispersed in water is obtained by polymerizing the raw material monomer of the binder resin by an emulsion polymerization method using an aqueous solvent. Can do. Commercially available emulsions may be used as the emulsion, for example, Polydurex series manufactured by Asahi Kasei Chemicals Corporation.
In addition, although there is no restriction | limiting in particular in the mass ratio of binder resin in 100 mass% of emulsion, Preferably it shall be about 20-65 mass%.
このようにして得られる塗料組成物は、水溶性アミン化合物によってｐＨ値を上記範囲内に容易に調整できるので、塗料組成物中のフェノールフタレインによって赤く着色している。該塗料組成物を対象物の被塗布面に塗布した直後は、塗膜は赤く着色しているので、塗布面と未塗布面との境界が目視にて容易に判断でき、塗り忘れや塗り斑を防止できる。そして、塗膜中の水溶性アミン化合物や水分の揮発により、塗膜のｐＨ値が中性側に移動してフェノールフタレインが無色に変化することによって、塗膜が脱色し、クリヤーな塗膜が得られる。
塗膜の脱色が完了するのに要する時間は、温度や湿度などの周囲の環境によって異なるが、本発明の塗料組成物を用いれば、塗布後３分〜２４時間の短時間で塗膜の脱色が完了する。
The coating composition obtained in this way is easily colored in red by phenolphthalein in the coating composition because the pH value can be easily adjusted within the above range by the water-soluble amine compound. Immediately after the coating composition is applied to the coated surface of the object, the coating film is colored red, so that the boundary between the coated surface and the uncoated surface can be easily determined visually, so Can be prevented. Then, due to the volatilization of water-soluble amine compounds and moisture in the coating film, the pH value of the coating film moves to the neutral side and the phenolphthalein changes to colorless. Is obtained.
The time required to complete the decolorization of the coating film varies depending on the surrounding environment such as temperature and humidity, but if the coating composition of the present invention is used, the coating film can be decolorized in a short time of 3 minutes to 24 hours after application. Is completed.
光触媒機能を利用した従来の塗料を対象物の被塗布面に塗布した場合、直射日光が当たりにくい部位では直射日光が当たる部位に比べて有機系着色剤が分解されにくく、塗膜の脱色が完了するのに数日〜数週間の時間が必要であった。そのため、無色部分と着色部分との色斑が長時間続くこととなり、外観上問題があった。
しかし、本発明であれば、塗膜の脱色は塗膜中の水溶性アミン化合物や水分の揮発性に依存するので、塗膜形成の部位に関係なく均一に脱色できる。また、短時間で塗膜の脱色が完了するので、無色部分と着色部分との色斑が長時間続くことを抑制できる。
When a conventional paint that uses a photocatalytic function is applied to the coated surface of an object, the organic colorant is less likely to be decomposed in areas where it is difficult to be exposed to direct sunlight than in areas where it is exposed to direct sunlight, and the decolorization of the coating is completed It took several days to weeks. Therefore, the color spots of the colorless portion and the colored portion last for a long time, and there is a problem in appearance.
However, according to the present invention, the decolorization of the coating film depends on the water-soluble amine compound and the volatility of moisture in the coating film, so that it can be uniformly decolored regardless of the site of coating film formation. Moreover, since decoloration of a coating film is completed in a short time, it can suppress that the color spot of a colorless part and a colored part continues for a long time.
さらに、本発明の塗料組成物であれば、光触媒塗料に限定されないので、幅広い用途が期待できる。ただし、本発明の塗料組成物中に光触媒粒子を含有させれば、塗膜に残留する水溶性アミン化合物や、フェノールフタレインを分解するので、脱色時間が早まると共に、得られる塗膜に防汚性機能を付与させることができるで、より有用な光触媒塗料が得られることは言うまでもない。 Furthermore, since the coating composition of the present invention is not limited to a photocatalytic coating, a wide range of uses can be expected. However, if the photocatalyst particles are contained in the coating composition of the present invention, the water-soluble amine compound remaining in the coating film and phenolphthalein are decomposed, so the decolorization time is accelerated and the resulting coating film is antifouling. It is needless to say that a more useful photocatalyst coating can be obtained because it can impart an sexual function.
なお、本発明の塗料組成物を保存する際は、水溶性アミン化合物や水分が蒸発しないように密閉容器に保管するのが好ましい。顔料として光触媒粒子をさらに含有させた場合は、遮光性の密閉容器に保管するのが好ましい。 When the coating composition of the present invention is stored, it is preferably stored in a sealed container so that the water-soluble amine compound and moisture do not evaporate. When the photocatalyst particles are further contained as a pigment, it is preferably stored in a light-shielding sealed container.
また、本発明の塗料組成物の塗布方法としては、刷毛、ローラ、エアスプレー、エアレススプレーなどの通常の方法により行うことができる。塗布の際には、事前に対象物の被塗布面に存在する埃や汚れなどを除去して清潔な状態にするのがよい。さらに、対象物の材質の伸縮に追従するよう、乾燥後の塗膜の膜厚が薄くなるように塗布するのが好ましい。乾燥後の塗膜の膜厚は１〜２０μｍが好ましく、１〜１０μｍがより好ましい。 Moreover, as a coating method of the coating composition of this invention, it can carry out by normal methods, such as a brush, a roller, an air spray, an airless spray. At the time of application, it is preferable to remove dust and dirt existing on the surface to be applied of the object in advance to make it clean. Furthermore, it is preferable to apply so that the film thickness of the coating film after drying becomes thin so as to follow the expansion and contraction of the material of the object. 1-20 micrometers is preferable and, as for the film thickness of the coating film after drying, 1-10 micrometers is more preferable.
また、本発明の塗料組成物を塗布する対象物の材質としては、金属、モルタル、コンクリート、セメント、木材、プラスチック、ガラスなどが挙げられる。
また、上記の材質からなる対象物の表面に、他の塗料を塗布して塗膜を形成させた後に、本発明の塗料組成物を塗布してもよい。
In addition, examples of the material of the object to which the coating composition of the present invention is applied include metal, mortar, concrete, cement, wood, plastic, and glass.
Further, the coating composition of the present invention may be applied after another coating is applied to the surface of the object made of the above material to form a coating film.
以上説明したように、本発明の塗料組成物はフェノールフタレインの特性を活かしており、水溶性アミン化合物で塗料組成物のｐＨ値を所望の値に調整することでフェノールフタレインを赤く呈色させ、塗料組成物を赤く着色させている。そのため、塗布面と未塗布面との境界が目視にて容易に判断できるので、塗り忘れや塗り斑を防止できる。そして、塗膜中の水溶性アミン化合物の揮発により塗膜のｐＨ値が中性側に移動することや、水分の揮発によりイオンが消失することによって、フェノールフタレインが無色に変化することによって、塗膜が脱色し、クリヤーな塗膜が得られる。
また、本発明は、塗膜の脱色において光触媒機能を利用していないので、光触媒塗料に限定されない。
As described above, the coating composition of the present invention takes advantage of the characteristics of phenolphthalein, and the phenolphthalein is colored red by adjusting the pH value of the coating composition to a desired value with a water-soluble amine compound. The coating composition is colored red. Therefore, since the boundary between the coated surface and the uncoated surface can be easily determined visually, forgetting to paint or smearing can be prevented. And, the pH value of the coating film moves to the neutral side due to volatilization of the water-soluble amine compound in the coating film, and the phenolphthalein changes to colorless by the disappearance of ions due to the volatilization of moisture. The paint film is decolored and a clear paint film is obtained.
Moreover, since this invention does not utilize the photocatalyst function in the decoloring of a coating film, it is not limited to a photocatalyst coating material.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されない。なお、例中「％」とは「質量％」を示す。
［実施例１］
＜塗料組成物の調製＞
バインダー樹脂としてアクリル−シリコーン樹脂（旭化成ケミカルズ社製、「ポリデュレックスＧ−６５９」固形分４２％）３３．０ｇに、顔料として光触媒粒子（石原産業社製、「ＳＴ−０１」）１．３ｇ、造膜助剤（イーストマンケミカルジャパン社製、「テキサノール」）４．０ｇ、消泡剤（ビックケミー・ジャパン社製、「ＢＹＫ−０２８」）０．１ｇ、および水５９．０ｇを加え、固形分１６％の混合物を得た。
この混合物に、水溶性アミン化合物として２−アミノ−２−メチル−１−プロパノール（ダウ・ケミカル日本社製、「ＡＭＰ−９０」、分子量：８９、沸点：１３３℃）０．６ｇを添加してｐＨ値を１０．０付近に調整した。次いで、３％フェノールフタレイン／イソプロピルアルコール溶液２．０ｇ（フェノールフタレインの固形分換算で０．０６ｇ）を添加し、赤く着色した塗料組成物（１００ｇ）を得た。
なお、ｐＨ値はｐＨメータ（堀場製作所社製、「ｐＨメータＦ−２１」）を用いて測定した。得られた塗料組成物のｐＨ値を表１に示す。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. In the examples, “%” means “% by mass”.
[Example 1]
<Preparation of coating composition>
33.0 g of acrylic-silicone resin (manufactured by Asahi Kasei Chemicals Co., Ltd., “Polydurex G-659”, solid content 42%) as a binder resin, 33.0 g, 1.3 g of photocatalyst particles (manufactured by Ishihara Sangyo Co., Ltd., “ST-01”), 4.0 g of a film-forming aid (manufactured by Eastman Chemical Japan, “Texanol”), 0.1 g of an antifoaming agent (manufactured by BYK Japan, “BYK-028”), and 59.0 g of water were added, and the solid content A 16% mixture was obtained.
To this mixture, 0.6 g of 2-amino-2-methyl-1-propanol (manufactured by Dow Chemical Japan, “AMP-90”, molecular weight: 89, boiling point: 133 ° C.) is added as a water-soluble amine compound. The pH value was adjusted to around 10.0. Subsequently, 2.0 g of a 3% phenolphthalein / isopropyl alcohol solution (0.06 g in terms of solid content of phenolphthalein) was added to obtain a red-colored coating composition (100 g).
The pH value was measured using a pH meter (Horiba, Ltd., “pH meter F-21”). The pH value of the obtained coating composition is shown in Table 1.
＜評価＞
アルミニウム製平板（７ｃｍ×１５ｃｍ）上に、プライマー（藤倉化成社製、「アクレタンＭ」、白色）を塗布し、乾燥させた基材に、得られた塗料組成物をスプレー塗布し（塗布量：６０ｇ／ｍ２）、試験体を作成した。乾燥後の塗膜の膜厚は５μｍであった。
塗料組成物の塗布後から、塗膜の脱色が完了するまでに要した時間（脱色時間）を計測した。結果を表１に示す。
また、塗料組成物を基材上に塗布する際の作業性について、以下の評価基準にて判断した。結果を表１に示す。
○：塗り忘れや塗り斑を目視にて判断でき作業性が良好であり、脱色、乾燥後の塗膜に変化が認められず、クリヤーな塗膜が得られた。
△：塗り忘れや塗り斑を目視にて判断でき作業性が良好であるが、脱色、乾燥後の塗膜が黄変したり、タック感が残ったりした。
×：塗り忘れや塗り斑を目視にて判断するのが困難である。
なお、脱色、乾燥後の塗膜の変化は、目視にて判断した。また、タック感は、塗料組成物を塗布した直後から２４時間経過後の塗膜を手指で触れて、タック感が残っているかどうかを判断した。
<Evaluation>
On a flat plate made of aluminum (7 cm × 15 cm), a primer (manufactured by Fujikura Kasei Co., Ltd., “Acretan M”, white) is applied, and the resulting coating composition is spray applied onto the dried substrate (application amount: 60 g / m 2 ), a test specimen was prepared. The film thickness of the coating after drying was 5 μm.
The time (decoloring time) required from the application of the coating composition to the completion of decoloring of the coating film was measured. The results are shown in Table 1.
Moreover, the workability | operativity at the time of apply | coating a coating composition on a base material was judged on the following evaluation criteria. The results are shown in Table 1.
A: Forgetting to paint or spotted spots can be judged visually, workability is good, no change is observed in the coating film after decolorization and drying, and a clear coating film is obtained.
Δ: Forgetting to paint or smearing can be judged visually, and the workability is good, but the coating film after decolorization and drying has turned yellow, or the tackiness remains.
X: It is difficult to visually judge forgetting to paint or smears.
In addition, the change of the coating film after decoloring and drying was judged visually. The tackiness was determined by touching the coating film after 24 hours from immediately after applying the coating composition with a finger to determine whether or not the tackiness remained.
［実施例２〜８及び参考例９，１０］
表１に示すように、水溶性アミン化合物の種類とその添加量、および３％フェノールフタレイン／イソプロピルアルコール溶液の添加量（フェノールフタレインの固形分換算量）を変化させた以外は、実施例１と同様にして塗料組成物を調製し、評価を実施した。結果を表１に示す。
[Examples 2 to 8 and Reference Examples 9 and 10]
As shown in Table 1, Examples except that the kind of water-soluble amine compound and its addition amount, and the addition amount of 3% phenolphthalein / isopropyl alcohol solution (the amount of phenolphthalein in terms of solid content) were changed. A coating composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 1.
［比較例１、４〜６］
表１に示すように、水溶性アミン化合物の種類、およびその添加量を変化させた以外は、実施例１と同様にして塗料組成物を調製し、評価を実施した。結果を表２に示す。
[Comparative Examples 1, 4-6]
As shown in Table 1, a coating composition was prepared and evaluated in the same manner as in Example 1 except that the type of water-soluble amine compound and the amount added were changed. The results are shown in Table 2.
［比較例２、３］
水溶性アミン化合物の代わりに、表１に示す非水溶性アミン化合物を用いた以外は、実施例１と同様にして塗料組成物を調製し、評価を実施した。結果を表２に示す。
[Comparative Examples 2 and 3]
A coating composition was prepared and evaluated in the same manner as in Example 1 except that the water-insoluble amine compound shown in Table 1 was used instead of the water-soluble amine compound. The results are shown in Table 2.
表１、２から明らかなように、各実施例で得られた塗料組成物を使用することにより、塗り忘れや塗り斑を目視にて判断でき作業性が良好であった。また、水溶性アミン化合物や３％フェノールフタレイン／イソプロピルアルコール溶液の添加量が少なくなると、塗膜の脱色時間が短くなった。
なお、実施例５、６では、水溶性アミン化合物の添加量を実施例１〜４に比べて増やしたので、それに伴い水分の揮発によるイオンの消失に時間がかかり、脱色時間は長くなったが、実施例５、６で用いた水溶性アミン化合物は揮発性が良好なので、脱色、乾燥後の塗膜は黄変したりタック感が残ったりすることはなかった。
As is clear from Tables 1 and 2, by using the coating composition obtained in each example, forgetting to paint or smearing could be judged visually, and workability was good. In addition, when the amount of the water-soluble amine compound or 3% phenolphthalein / isopropyl alcohol solution was decreased, the decolorization time of the coating film was shortened.
In Examples 5 and 6, the amount of the water-soluble amine compound added was increased compared to Examples 1 to 4, and accordingly, it took time for the disappearance of ions due to the volatilization of water, and the decolorization time became longer. Since the water-soluble amine compounds used in Examples 5 and 6 have good volatility, the coating after decolorization and drying did not turn yellow or remain tacky.
また、参考例９で得られた塗料組成物は、水酸基を２つ有する水溶性アミン化合物を用いたため、揮発性が低下し、フェノールフタレイン（固形分換算）の含有量が同量の実施例１に比べて、脱色時間が長くなった。また、参考例９で用いた水溶性アミン化合物は沸点が２４７℃と高かったため、塗料組成物のｐＨ値を所望の値に調整するために添加量を増やす必要があったが、添加量を３．５ｇに増やしても塗料組成物のｐＨ値は９．８であった。そのため、僅かな量の水溶性アミン化合物の揮発で塗膜のｐＨ値は中性側に移動したため、脱色が完了した後の塗膜中にも多量の水溶性アミン化合物が残留し、脱色、乾燥後の塗膜が黄変した。
参考例１０で得られた塗料組成物は、水酸基を３つ有する水溶性アミン化合物を用いたため、参考例９よりもさらに揮発性が低下し、脱色時間が長くなった。また、水溶性アミン化合物の沸点が３３５℃と高かったため、参考例９よりもさらに添加量を増やす必要があり、脱色、乾燥後の塗膜が黄変すると共に、タック感が残っていた。
Moreover, since the coating composition obtained in Reference Example 9 used a water-soluble amine compound having two hydroxyl groups, the volatility was lowered and the content of phenolphthalein (in terms of solid content) was the same. Compared to 1, the decolorization time was longer. Further, since the water-soluble amine compound used in Reference Example 9 had a boiling point as high as 247 ° C., it was necessary to increase the addition amount in order to adjust the pH value of the coating composition to a desired value. Even when it was increased to 0.5 g, the pH value of the coating composition was 9.8. Therefore, since the pH value of the coating moved to the neutral side due to the volatilization of a small amount of the water-soluble amine compound, a large amount of the water-soluble amine compound remained in the coating after the decolorization was completed. The later coating film turned yellow.
Since the coating composition obtained in Reference Example 10 used a water-soluble amine compound having three hydroxyl groups, the volatility was further lowered and the decolorization time was longer than that in Reference Example 9. Moreover, since the boiling point of the water-soluble amine compound was as high as 335 ° C., it was necessary to increase the amount of addition more than in Reference Example 9, and the coating film after decolorization and drying turned yellow, and the tackiness remained.
一方、比較例１、４で得られた塗料組成物は、沸点の低い水溶性アミン化合物を用いたため、塗布前は赤く着色していたが、塗布した直後から水溶性アミン化合物が揮発してしまい、塗膜が直ちに脱色して、塗り忘れや塗り斑を目視にて判断しにくかった。
比較例２、３で得られた塗料組成物は、非水溶性アミン化合物を用いたため、塗料組成物のｐＨ値が所望の値に調整できず、赤く着色しなかった。そのため、塗り忘れや塗り斑を目視にて判断しにくかった。
比較例５で得られた塗料組成物は、水溶性アミン化合物の添加量が少なかったため、ｐＨ値が所望の値にならなかった。そのため、塗料組成物は若干赤く着色していたが、僅かな量の水溶性アミン化合物が揮発しただけでも直ちにｐＨ値が中性側に移動しやすい状態であったため、塗布した直後から塗膜が脱色し、塗り忘れや塗り斑を目視にて判断しにくかった。
比較例６で得られた塗料組成物は、水溶性アミン化合物の添加量が少なかったため、ｐＨ値が所望の値にならなかった。そのため、フェノールフタレインが赤く呈色せず、塗料組成物も赤く着色せず、塗り忘れや塗り斑を目視にて判断しにくかった。
On the other hand, the coating compositions obtained in Comparative Examples 1 and 4 were colored red before coating because they used a low-boiling water-soluble amine compound, but the water-soluble amine compound volatilized immediately after coating. The coating film was immediately decolored, and it was difficult to visually determine forgetting to paint or smears.
Since the coating composition obtained in Comparative Examples 2 and 3 used a water-insoluble amine compound, the pH value of the coating composition could not be adjusted to a desired value and did not color red. For this reason, it was difficult to visually determine forgetting to paint or uneven spots.
The coating composition obtained in Comparative Example 5 did not have a desired pH value because the amount of water-soluble amine compound added was small. Therefore, although the coating composition was slightly colored in red, the pH value easily moved to the neutral side even if only a small amount of the water-soluble amine compound volatilized. It was difficult to judge forgetting to paint or smear by visually removing the color.
In the coating composition obtained in Comparative Example 6, the pH value did not reach the desired value because the amount of the water-soluble amine compound added was small. For this reason, phenolphthalein did not color red, and the coating composition did not color red, making it difficult to visually determine forgetting to paint or spots.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007212868A JP5386073B2 (en) | 2007-08-17 | 2007-08-17 | Water-based clear coating composition and method for producing coating film using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007212868A JP5386073B2 (en) | 2007-08-17 | 2007-08-17 | Water-based clear coating composition and method for producing coating film using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009046555A JP2009046555A (en) | 2009-03-05 |
| JP5386073B2 true JP5386073B2 (en) | 2014-01-15 |
Family
ID=40499076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007212868A Active JP5386073B2 (en) | 2007-08-17 | 2007-08-17 | Water-based clear coating composition and method for producing coating film using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5386073B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020005492A1 (en) * | 2018-06-25 | 2020-01-02 | Dow Global Technologies Llc | Primer composition |
| JP2022056097A (en) * | 2020-09-29 | 2022-04-08 | 日本ペイントホールディングス株式会社 | Light-decolorizable coating material composition for clear coated film, clear coated film, article, and method of forming clear coated film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002285098A (en) * | 2001-03-27 | 2002-10-03 | Konishi Co Ltd | Bleachable spread coating resin composition |
| JP4518567B2 (en) * | 2007-03-09 | 2010-08-04 | Ｔｏｔｏ株式会社 | Coating liquid |
-
2007
- 2007-08-17 JP JP2007212868A patent/JP5386073B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009046555A (en) | 2009-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3910032B1 (en) | Antimicrobial paint composition and related methods | |
| EP1144332B1 (en) | Forming or coating material and utilisation thereof | |
| RU2377267C2 (en) | Coating material | |
| WO2007025914A1 (en) | Aqueous composition for external, internal, fronts and roof coverings | |
| US4274884A (en) | Method of removing wallpaper | |
| JP2008208338A (en) | Aqueous liquid coating | |
| EP2152816B1 (en) | Paint remover | |
| JP5386073B2 (en) | Water-based clear coating composition and method for producing coating film using the same | |
| JP4518567B2 (en) | Coating liquid | |
| CA2597951A1 (en) | Reflective decorative surface coating and a decorative water-borne surface coating system having at least one basecoat | |
| EP0897964B1 (en) | Proctective polymer film to remove soil and process for producing the same | |
| JP2012503050A (en) | Paint material containing basic additives | |
| JP7231838B2 (en) | Method for producing coating composition | |
| JP2002088312A (en) | Seaweedproof and mildewproof coating composition | |
| JP2977768B2 (en) | Aqueous emulsion paint | |
| HU185649B (en) | Method for producing water-repellent and vapour-permeable coat pigments particularly for building frontages | |
| WO2022070870A1 (en) | Light-decolorizable coating composition for clear coating film, clear coating film, article, and method for forming clear coating film | |
| JP2002206074A (en) | Water-base coating composition | |
| JP5576227B2 (en) | Painting method | |
| KR100583807B1 (en) | Water-based paint composition | |
| GB2418924A (en) | Weathered-effect composition | |
| JP2019155357A (en) | Coating film formation method | |
| JP2008127513A (en) | Hydrophilic inorganic paint | |
| WO2007012106A1 (en) | Sacrificial anti-graffiti coating composition | |
| JPH1129726A (en) | Oil-stain-resistant coating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100511 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120619 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120808 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20121023 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131007 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5386073 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |